U.S. patent number 9,221,030 [Application Number 14/000,150] was granted by the patent office on 2015-12-29 for method for producing water-absorbent resin.
This patent grant is currently assigned to SUMITOMO SEIKA CHEMICALS CO., LTD.. The grantee listed for this patent is Noriko Honda, Kimihiko Kondo, Ayaka Watanabe. Invention is credited to Noriko Honda, Kimihiko Kondo, Ayaka Watanabe.
United States Patent |
9,221,030 |
Honda , et al. |
December 29, 2015 |
Method for producing water-absorbent resin
Abstract
A method for producing a water-absorbent resin includes a
polymerization step of polymerizing a polymerizable component
containing a water-soluble ethylenically unsaturated monomer
dissolved in water using a water-soluble azo-type radical
polymerization initiator to obtain a reaction system including a
water-absorbent resin precursor, and a dehydration step of removing
water from the reaction system by heating. In the dehydration step,
a water-soluble radical polymerization initiator is added to the
reaction system at any first dehydration stage when the residual
water rate calculated by the formula (1) is 50% or more, and a
reducing substance is added to the reaction system at any second
dehydration stage when the residual water rate decreases from that
at the first dehydration stage by 10% or more. According to this
production method, a water-absorbent resin having satisfactory
water-absorption capacity can be produced while suppressing the
content of residual monomers.
.times..times..times..times..times..times..times..times..times.-
.times..times..times..times..times..times..times..times..times..times..tim-
es..times..times..times..times..times..times..times..times..times..times..-
times. ##EQU00001##
Inventors: |
Honda; Noriko (Kakogawa,
JP), Watanabe; Ayaka (Saitama, JP), Kondo;
Kimihiko (Himeji, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Honda; Noriko
Watanabe; Ayaka
Kondo; Kimihiko |
Kakogawa
Saitama
Himeji |
N/A
N/A
N/A |
JP
JP
JP |
|
|
Assignee: |
SUMITOMO SEIKA CHEMICALS CO.,
LTD. (Hyogo, JP)
|
Family
ID: |
46930598 |
Appl.
No.: |
14/000,150 |
Filed: |
March 12, 2012 |
PCT
Filed: |
March 12, 2012 |
PCT No.: |
PCT/JP2012/056300 |
371(c)(1),(2),(4) Date: |
August 16, 2013 |
PCT
Pub. No.: |
WO2012/132861 |
PCT
Pub. Date: |
October 04, 2012 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
|
US 20130324396 A1 |
Dec 5, 2013 |
|
Foreign Application Priority Data
|
|
|
|
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Mar 28, 2011 [JP] |
|
|
2011-070727 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F
2/20 (20130101); C08F 4/04 (20130101); C08F
20/06 (20130101); C08F 6/006 (20130101); C08F
6/008 (20130101); B01J 20/261 (20130101); C08F
2/14 (20130101); A61L 15/60 (20130101); C08F
6/006 (20130101); C08L 33/02 (20130101); C08F
6/008 (20130101); C08L 33/02 (20130101); A61L
15/60 (20130101); C08L 33/02 (20130101); A61L
15/60 (20130101); C08L 33/08 (20130101); A61L
15/60 (20130101); C08L 33/10 (20130101) |
Current International
Class: |
B01J
20/26 (20060101); C08F 4/04 (20060101); C08F
2/20 (20060101); C08F 20/06 (20060101); C08F
6/00 (20060101); A61L 15/60 (20060101) |
Field of
Search: |
;502/402 ;526/317.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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101479297 |
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Jul 2009 |
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CN |
|
101765637 |
|
Jun 2010 |
|
CN |
|
101835814 |
|
Sep 2010 |
|
CN |
|
1 882 701 |
|
Jan 2008 |
|
EP |
|
2 599 795 |
|
Jun 2013 |
|
EP |
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2 599 795 |
|
Jun 2013 |
|
EP |
|
64-062317 |
|
Mar 1989 |
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JP |
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64-62317 |
|
Mar 1989 |
|
JP |
|
2001-2726 |
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Jan 2001 |
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JP |
|
2001-11106 |
|
Jan 2001 |
|
JP |
|
2002-105125 |
|
Apr 2002 |
|
JP |
|
2002-105125 |
|
Apr 2002 |
|
JP |
|
2002-241428 |
|
Aug 2002 |
|
JP |
|
2003-206305 |
|
Jul 2003 |
|
JP |
|
2006-176570 |
|
Jul 2006 |
|
JP |
|
2008-7567 |
|
Jan 2008 |
|
JP |
|
2008-133396 |
|
Jun 2008 |
|
JP |
|
2008-133396 |
|
Jun 2008 |
|
JP |
|
WO 03/059962 |
|
Jul 2003 |
|
WO |
|
Other References
English translation of International Preliminary Report on
Patentability and Written Opinion mailed Oct. 10, 2013. cited by
applicant .
International Search Report issued in Apr. 17, 2013, in PCT
International Application No. PCT/JP2012/056300. cited by applicant
.
Chinese Search Report dated Dec. 2, 2014 issued in Chinese Patent
Application No. 201280015717.2. cited by applicant .
Search Report issued in SG Application No. 2013064993 dated Nov.
13, 2014. cited by applicant .
Supplementary European Search Report dated Oct. 1, 2014, issued in
European Patent Application No. 12765406.9. cited by applicant
.
Written Opinion issued in SG 2013064993 dated Nov. 13, 2014. cited
by applicant.
|
Primary Examiner: Harlan; Robert
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. A method for producing a water-absorbent resin, comprising: a
polymerization step of polymerizing a polymerizable component
containing a water-soluble ethylenically unsaturated monomer
dissolved in water using a water-soluble azo-type radical
polymerization initiator to obtain a reaction system comprising a
water-absorbent resin precursor, and a dehydration step of removing
water from the reaction system by heating, wherein, in the
dehydration step, a water-soluble radical polymerization initiator
is added to the reaction system at any first dehydration stage when
the residual water rate calculated by the following formula (1) is
50% or more, and a reducing substance is added to the reaction
system at any second dehydration stage when the residual water rate
decreases from that at the first dehydration stage by 10% or more,
wherein the residual water rate (%) is determined by the following
Formula (1): .times..times. ##EQU00007##
2. The method for producing a water-absorbent resin according to
claim 1, wherein the polymerizable component is polymerized by a
reversed-phase suspension polymerization method in the
polymerization step.
3. The method for producing a water-absorbent resin according to
claim 2, wherein the polymerizable component is further added to be
polymerized to a slurry obtained by progress of the polymerization
of the polymerizable component.
4. The method for producing a water-absorbent resin according to
claim 3, wherein the addition of the polymerizable component to the
slurry and the polymerization are repeated.
5. The method for producing a water-absorbent resin according to
claim 1, wherein the water-soluble azo-type radical polymerization
initiator is at least one selected from the group consisting of
2,2'-azobis(2-amidinopropane)dihydrochloride,
2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochlori-
de, and
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate-
.
6. The method for producing a water-absorbent resin according to
claim 1, wherein the water-soluble radical polymerization initiator
is at least one selected from the group consisting of potassium
persulfate, sodium persulfate, and
2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride.
7. The method for producing a water-absorbent resin according to
claim 1, wherein the reducing substance is at least one selected
from the group consisting of sulfurous acid, a sulfite, hydrogen
sulfite and a bisulfite.
8. The method for producing a water-absorbent resin according to
claim 1, wherein the amount of the water-soluble radical
polymerization initiator added to the reaction system is 0.01 to
0.15 mol % of the total amount of the water-soluble ethylenically
unsaturated monomer used in the polymerization step.
9. The method for producing a water-absorbent resin according to
claim 1, wherein the amount of the reducing substance added to the
reaction system is 0.0001 to 0.002 mol % of the total amount of the
water-soluble ethylenically unsaturated monomer used in the
polymerization step.
10. The method for producing a water-absorbent resin according to
claim 1, wherein the water-absorbent resin precursor is subjected
to a post-crosslinking treatment in the dehydration step.
11. A water-absorbent resin obtainable by the method for producing
a water-absorbent resin as defined in claim 1, wherein the content
of residual monomers is 100 ppm or less, and which is in powdery
form having a mass average particles size of 200 to 600 .mu.m and
has a retention capacity of saline solution of 40 to 60 g/g and an
absorption capacity of saline solution under a load of 4.14 kPa of
20 ml/g or more.
12. A hygienic material comprising a liquid-permeable sheet, a
liquid-impermeable sheet, and an absorbent material retained
between these sheets, wherein the absorbent material comprises the
water-absorbent resin as defined in claim 11.
13. The hygienic material according to claim 12, wherein the
absorbent material is a composite of the water-absorbent resin and
a hydrophilic fiber.
Description
TECHNICAL FIELD
The present invention relates to a method for producing a
water-absorbent resin, in particular, to a method for producing a
water-absorbent resin by polymerizing polymerizable component
containing a water-soluble ethylenically unsaturated monomer
dissolved in water using a water-soluble azo-type radical
polymerization initiator.
BACKGROUND ART
A water-absorbent resin is widely used in hygienic materials such
as disposable diapers and sanitary napkins, commodities such as pet
sheets, and industrial materials such as water blocking materials
for cable. While many types of water-absorbent resins are known in
accordance with various applications, a water-absorbent resin made
of a polymer of water-soluble ethylenically unsaturated monomer is
mainly used in hygienic materials such as disposable diapers and
sanitary napkins. For the water-absorbent resin made of a polymer
of water-soluble ethylenically unsaturated monomer used in a
hygienic material, high safety is generally required due to a
possibility of direct contact to the human body, and absorption
capacity that can rapidly and stably absorb and retain a large
amount of body fluids when contacting to body fluids such as urine
and blood is also required. Particularly, recent hygienic materials
tend to be made thinner for comfortableness in wearing and
portability, and thus are urged to use a smaller amount of the
water-absorbent resin and, at the same time, to increase absorption
capacity. Therefore, higher water-absorption capacity of a
water-absorbent resin itself is now required.
A water-absorbent resin made of a polymer water-soluble
ethylenically unsaturated monomer can achieve higher water
absorption generally by lowering the degree of crosslinking.
However, this type of water-absorbent resin is often produced by
polymerizing a water-soluble ethylenically unsaturated monomer
using a persulfate as a polymerization initiator. In this case,
self-crosslinking is likely to progress in the produced
water-absorbent resin, thus it is difficult to obtain a
water-absorbent resin with high water-absorption capacity. For the
improvement in this respect, Patent Literature 1 describes that an
azo-type compound capable of suppressing self-crosslinking is used
as a polymerization initiator in place of a persulfate. However,
since the polymerization rate of a water-soluble ethylenically
unsaturated monomer is less likely to rise in the case of using an
azo-type compound as a polymerization initiator, a lot of unreacted
monomers remain in the produced water-absorbent resin. Furthermore,
the amount of unreacted monomers in the water-absorbent resin tends
to increase by partial decomposition of the water-absorbent resin
in the dehydration step of removing water by heating from a
reaction system containing the produced water-absorbent resin. When
the water-absorbent resin containing unreacted monomers and
monomers produced by decomposition of part of the ter-absorbent
resin (hereinafter, these monomers ray be collectively-referred to
as "residual monomers") is used in a hygienic material, it may
cause skin problems such, as rush and inflammation on a user.
Therefore, a method for suppressing the content of residual
monomers in a water-absorbent resin is suggested. For example,
Patent Literature 2 describes a method of adding a radical
polymerization initiator before drying or during drying a slurry
containing a water-absorbent resin obtained by polymerizing a
water-soluble ethylenically unsaturated monomer by a reversed-phase
suspension polymerization method. Also, Patent Literature 3
describes a method of adding a reducing substance such as a sulfite
and a method of adding a prescribed azo compound together with a
reducing substance, after the polymerization of a water-soluble
ethylenically unsaturated monomer.
However, the water-absorbent resin produced in accordance with
these methods has a defect in water-absorption capacity, which is
an essential quality required for a water-absorbent resin, while
the content of residual monomers is suppressed.
PRIOR ART LITERATURES
Patent Literatures
Patent Literature 1: Japanese Patent Application Laid-Open No.
2006-176570 Patent Literature 2: Japanese Patent Application
Laid-Open No. 2002-105125 Patent Literature 3: Japanese Patent
Application Laid-Open No. 64-62317
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
An object of the present invention is to produce a water-absorbent
resin that shows satisfactory water-absorption capacity while
suppressing the content of residual monomers.
Means for Solving the Problems
A method for producing a water-absorbent resin according to the
present invention includes a polymerization step of polymerizing a
polymerizable component containing water-soluble ethylenically
unsaturated monomer dissolved in water using a water-soluble
azo-type radical polymerization initiator to obtain a reaction
system containing water-absorbent resin precursor, and a
dehydration step of removing water from the reaction system by
heating. In the dehydration step, a water-soluble radical
polymerization initiator is added to the reaction system at any
first dehydration stage when the residual water rate calculated by
the following formula (1) is 50% or more, and a reducing substance
is added to the reaction system at any second dehydration stage
when the residual water rate decreases from that at the first
dehydration stage by 10% or more.
.times..times..times..times..times..times..times..times..times..times..ti-
mes..times..times..times..times..times..times..times..times..times..times.-
.times..times..times..times..times..times..times..times..times..times..tim-
es..times..times. ##EQU00002##
In the polymerization step of this production method, it is usually
preferred that the polymerizable component is polymerized by a
reversed-phase suspension polymerization method. In this
polymerization method, the polymerizable component may be further
added to be polymerized, to a slurry obtained by progress of the
polymerization of the polymerizable component. In this case, the
addition of the polymerizable component to the slurry and the
polymerization may be repeated.
The water-soluble azo-type radical polymerization initiator used in
the polymerization step of this production method is usually at
least one selected from the group consisting of
2,2'-azobis(2-amidinopropane)dihydrochloride,
2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochlori-
de, and
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate-
.
The water-soluble radical polymerization initiator used in the
dehydration step of this production method is usually at least one
selected from the group consisting of potassium persulfate, sodium
persulfate, and
2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride, and the
reducing substance is usually at least one selected from the group
consisting of sulfurous acid, a sulfite, hydrogen sulfite and a
bisulfite.
In the production method of the present invention, the amount of
the water-soluble radical polymerization initiator added to the
reaction system is usually preferably set to 0.01 to 0.15 mol % of
the total amount of the water-soluble ethylenically unsaturated
monomer used in the polymerization step. In addition, the amount of
the reducing substance added to the reaction system is usually
preferably set to 0.0001 to 0.002 mol % of the total amount of the
water-soluble ethylenically unsaturated monomer used in the
polymerization step.
In an embodiment of the production method of the present invention,
a water-absorbent resin precursor is subjected to a
post-crosslinking treatment in the dehydration step.
In the method for producing a water-absorbent resin according to
the present invention, since a water-soluble radical polymerization
initiator and a reducing substance are separately added in a
prescribed stage in this order in the dehydration step of the
reaction system, a water-absorbent resin having satisfactory
water-absorption capacity can be produced while suppressing the
content of residual monomers.
The present invention according to another standpoint is directed
to a water-absorbent resin, and this water-absorbent resin is
obtainable by the production method of the present invention. The
content of residual monomers in this water-absorbent resin is
usually 100 ppm or less. One embodiment of this water-absorbent
resin is it powdery form having a mass average particle size of 200
to 600 .mu.m, and has a retention capacity of saline solution of 40
to 60 g/g and an absorption capacity of saline solution under a
load of 4.14 kPa of 20 ml/g or more.
Since the water-absorbent resin of the present invention is
produced by the production method of the present invention, the
amount of residual monomers is small, and water-absorption capacity
is excellent.
The present invention according to still another standpoint is
directed to a hygienic material. This hygienic material includes a
liquid permeable sheet, a liquid impermeable sheet, and an
absorbent material retained between these sheets, and the absorbent
material contains the water-absorbent resin of the present
invention. The absorbent material is, for example, a composite of
the water-absorbent resin of the present invention and a
hydrophilic fiber.
The hygienic material of the present invention uses the
water-absorbent resin produced by the production method of the
present invention, thus is less likely to cause skin problems due
to residual monomers and has excellent water-absorption
capacity.
Other objects and effects of the present invention will be
mentioned in the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 A schematic view of an apparatus used in Examples for the
measurement of a water-absorption capacity under load.
EMBODIMENTS OF THE INVENTION
In the method for producing a water-absorbent resin according to
the present invention, first, a polymerizable component containing
a water-soluble ethylenically unsaturated monomer is polymerized to
prepare a water-absorbent resin (polymerization step). The
water-absorbent resin prepared herein is to be chemically treated
in the below-mentioned dehydration step, and thus termed as
"water-absorbent resin precursor" for the sake of convenience.
A water-soluble ethylenically unsaturated monomer used herein is
not particularly limited so long as it can be used in the
production of a water-absorbent resin, and examples thereof include
acrylic acid, methacrylic acid,
2-acrylamide-2-methylpropanesulfonic acid and alkali metal salts
thereof, 2-methacrylamide-2-methylpropanesulfonic acid and alkali
metal salts thereof, nonionic water-soluble ethylenically
unsaturated monomers, and amino group-containing water-soluble
ethylenically unsaturated monomers and quaternized products
thereof, and the like. In the examples, a lithium salt, a sodium
salt or a potassium salt is usually used as the alkali metal salt.
In addition, examples of the nonionic water-soluble ethylenically
unsaturated monomer include acrylamide, methacrylamide,
N,N-dimethylacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl
methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, and
the like. Furthermore, examples of the amino group-containing
water-soluble ethylenically unsaturated monomer include
diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
diethylaminopropyl acrylate, diethylaminopropyl methacrylate, and
the like.
The water-soluble ethylenically unsaturated monomer can be used in
combination of two or more kinds.
Examples of preferred water-soluble ethylenically unsaturated
monomers include acrylic acid and alkali metal salts thereof,
methacrylic acid and alkali metal salts thereof, acrylamide,
methacrylamide, and N,N-dimethylacrylamide since they are easily
available industrially. Examples of particularly preferred
water-soluble ethylenically unsaturated monomers include acrylic
acid, and alkali metal salts thereof and methacrylic acid and
alkali metal salts thereof since they can economically produce a
water-absorbent resin.
In the present invention, the water-soluble ethylenically
unsaturated monomer is dissolved in water and used as an aqueous
solution. The concentration of the water-soluble ethylenically
unsaturated monomer in an aqueous solution is usually preferably
set to 15% by mass or more and a saturated concentration or
less.
When the water-soluble ethylenically unsaturated monomer contains
an acid group, the aqueous solution of the water-soluble
ethylenically unsaturated monomer may be one in which the acid
group is neutralized by addition of an alkali metal compound. The
alkali metal compound used for this purpose is not particularly
limited, and is usually a hydroxide. As the alkali metal, lithium,
sodium or potassium is usually used, sodium or potassium is
preferably used, and sodium is particularly preferably used. The
neutralization degree achieved by addition of the alkali metal
compound is preferably set in the range of 10 to 100 mol % of the
acid group of the water-soluble ethylenically unsaturated monomer
before neutralization, from the viewpoint of increasing the
er-absorption rate with enhancing the osmotic pressure of the
obtained water-absorbent resin and not causing a problem in safety
of the water-absorbent resin by the presence of an excess alkali
metal compound.
The polymerizable component used in the polymerization step may be
composed only of the water-soluble ethylenically unsaturated
monomer or may contain an internal-crosslinking agent. Examples of
the internal-crosslinking agent used herein include polyvalent
glycidyl compounds such as ethylene diglycidyl ether, polyethylene
diglycidyl ether, glycerol polyglycidyl ether, diglycerol
polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene
glycol diglycidyl ether, propylene glycol dialycidyl ether,
polypropylene glycol diglycidyl ether, glycerol diglycidyl ether,
and polyglycerol diglycidyl ether. Among these, ethylene glycol
diglycidyl ether, polyethylene glycol diglycidyl ether, propylene
glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
glycerol diglycidyl ether or polyglycerol diglycidyl ether is
preferably used since a water-absorbent resin having a smaller
amount of water-soluble substance, which shows high
water-absorption capacity under load and excellent water-absorption
rate, is likely to be obtained. The internal-crosslinking agent can
be used in combination of two or more kinds.
The usage of the internal-crosslinking agent is not unconditionally
determined since it differs depending on the type, but is usually
preferably set to 0.000001 to 0.001 mol and more preferably set to
0.00001 to 0.01 mol, relative to 1 mol of the water-soluble
ethylenically unsaturated monomer, from the viewpoint of reducing
the water-soluble substance by achieving moderate crosslinking
while maintaining sufficient water-absorption capacity in the
intended water-absorbent resin.
The internal-crosslinking agent may be added to the aqueous
solution of the water-soluble ethylenically unsaturated monomer, or
may be added to the reaction system separately from the
water-soluble ethylenically unsaturated monomer.
In the polymerization of the polymerizable component containing a
water-soluble ethylenically unsaturated monomer, a water-soluble
azo-type radical polymerization initiator is used. Examples of the
usable water-soluble azo-type radical polymerization initiator
include 1-[(1-cyano-1-methylethyl)azo]formamide,
2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride,
2,2'-azobis[2-[N-(4-chlorophenyl)amidino]propane]dihydrochloride,
2,2'-azobis[2-[N-(4-hydroxyphenyl)amidino]propane]dihydrochloride,
2,2'-azobis-[2-(N-benzylamidino)propane]dihydrochloride,
2,2'-azobis[2-(N-allylamidino)propane]dihydrochloride,
2,2'-azobis(2-amidinopropane)dihydrochloride,
2,2'-azobis[2-[N-(2-hydroxyethyl)amidino]propane]dihydrochloride,
2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,
2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)dihydrochloride,
2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydro-
chloride,
2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihy-
drochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane],
2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyeth
yl]propionamide],
2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide],
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide],
2,2'-azobis(2-methylpropionamide)dihydrate,
4,4'-azobis-4-cyanovaleric acid,
2,2'-azobis[2-(hydroxymethyl)propionitrile],
2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate,
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate,
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and the like.
Among these, 2,2'-azobis(2-amidinopropane)dihydrochloride,
2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochlori-
de or
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate
is particularly preferably used since a water-absorbent resin
having a smaller amount of water-soluble substance and showing high
water-retention capacity is obtained.
The water-soluble azo-type radical polymerization initiator can be
used in combination of two or more kinds.
The polymerization method of the polymerizable component containing
a water-soluble ethylenically unsaturated monomer is not
particularly limited so long as it is a method capable of
polymerizing a water-soluble ethylenically unsaturated monomer as
an aqueous solution, and can be selected from the classic
polymerization methods such as an aqueous polymerization method, an
emulsion polymerization method, and a reversed-phase suspension
polymerization method.
In the case of the aqueous polymerization method, a reaction vessel
is charged with an aqueous solution of water-soluble ethylenically
unsaturated monomer, water-soluble azo-type radical polymerization
initiator, and optionally an internal-crosslinking agent, and
polymerization can be progressed by heating while stirring as
required. In the case of the reversed-phase suspension
polymerization method, at least one of those among a surfactant and
a polymeric protective colloid, an aqueous solution of a
water-soluble ethylenically unsaturated monomer, a water-soluble
azo-type radical polymerization initiator, and optionally an
internal-crosslinking agent are charged to a hydrocarbon solvent,
and polymerization can be progressed by heating while stirring.
The polymerization method preferred in the polymerization step is
the reversed-phase suspension polymerization method since precise
control of polymerization reaction is possible, and the particle
size of the resulting water-absorbent resin can be controlled in a
wide range. Hereinafter, the case of carrying out the
polymerization step by a reversed-phase suspension polymerization
method is described in more detail.
The hydrocarbon solvent used in the reversed-phase suspension
polymerization method is not particularly limited, and examples
thereof include aliphatic hydrocarbon solvents such as n-hexane
n-heptane and ligroin; alicyclic hydrocarbon solvents such as
cyclopentane, methylcyclopentane, cyclohexane and
methylcyclohexane; aromatic hydrocarbons such as benzene, toluene
and xylene; and the like. Among these, n-hexane, n-heptane or
cyclohexane is preferably used since they are easily available
industrially and inexpensive, and the quality is stable. The
hydrocarbon solvent can be used in combination of two or more
kinds.
The usage of the hydrocarbon solvent is usually preferably set to
50 to 600 parts by mass and more preferably set to 80 to 550 parts
by mass, relative to 100 parts by mass of the water-soluble
ethylenically unsaturated monomer, since it is easy to control the
polymerization temperature by removal of the heat of
polymerization.
Examples of the surfactant usable in the reversed-phase suspension
polymerization method include nonionic surfactants such as sorbitan
fatty acid esters, polyglyceryl fatty acid esters, sucrose fatty
acid esters, sorbitol fatty acid esters and polyoxyethylene alkyl
phenyl ethers; and anionic surfactants such as fatty acid salts,
alkylbenzene sulfonates, alkyl methyl taurates, polyoxyethylene
alkylphenyl ether sulfates and polyoxyethylene alkyl ether
sulfonates; and the like. Among these, a nonionic surfactant,
particularly, a sorbitan fatty acid ester, a polyglyceryl fatty
acid ester or a sucrose fatty acid ester is preferably used.
Examples of the polymeric protective colloid include ethyl
cellulose, ethylhydroxyethyl cellulose, polyethylene oxide, maleic
anhydride-modified polyethylene, maleic anhydride-modified
polybutadiene, a maleic anhydride-modified EPDM
(ethylene/propylene/diene/terpolymer), and the like.
In the reversed-phase suspension polymerization method, one of
those among the surfactant and the polymeric protective colloid may
be used, or both can be used in combination. The usage of the
surfactant and the polymeric protective colloid is preferably set
to 0.1 to 5 parts by mass and more preferably 0.2 to 3 parts by
mass, relative to 1.00 parts by mass of the water-soluble
ethylenically unsaturated monomer, from the viewpoint of stability
of a reversed-phase suspension polymerization system.
The usage of the water-soluble azo-type radical polymerization
initiator is preferably set to 0.00005 to 0.001 mol and more
preferably set to 0.0001 to 0.0008 mol, relative to 1 mol of the
water-soluble ethylenically unsaturated monomer, since the
polymerization reaction time can be shortened while preventing
sudden polymerization reaction.
The reaction temperature at the time of polymerization reaction is
usually preferably set to 20 to 110.degree. C. and more preferably
set to 40 to 90.degree. C. since the reaction can be smoothly
performed while easily removing the heat of polymerization, and
economical efficiency can be improved owing to shorter
polymerization time realized by rapid polymerization reaction. In
this case, the polymerization reaction time can be usually from 0.5
to 4 hours.
The polymerization by the reversed-phase suspension polymerization
method can be carried out in multiple stages by further adding the
polymerizable component stepwise at once or in several times to a
slurry obtained by progress of the polymerization of the
polymerizable component. When the temperature of the slurry is high
at the time of stepwise addition of the polymerizable component, it
is preferred that the slurry is once cooled to room temperature,
and then the polymerizable component is added. In addition, the
number of times (the number of stages) of the polymerization in
multi-stage polymerization is preferably set to two stages (the
number of times of further addition of the polymerizable component
is once) or three stages (the number of times of further addition
of the polymerizable component is twice) that can reasonably
enhance the productivity of the water-absorbent resin.
Next, the reaction system in which the polymerization reaction has
completed, specifically, the reaction system containing a
water-absorbent resin precursor, is heated, thereby removing water
from the reaction system (dehydration step). Examples of the
specific method for removing water from the reaction system include
(a) a method of externally heating the reaction system in which a
water-absorbent resin precursor is dispersed in a hydrocarbon
solvent, and removing water by azeotropic distillation, (b) a
method of separating a water-absorbent resin precursor from the
reaction system by decantation and drying the reaction system
containing the separated water water-absorbent resin precursor
under reduced pressure while heating to remove water, (c) a method
of separating a water-absorbent resin precursor using a filter and
drying the reaction system containing the separated water-absorbent
resin precursor under reduced pressure while heating to remove
water, and the like. Among these methods, the method of (a) is
suitably used as the operation is easy the reaction system contains
an organic solvent such as a hydrocarbon solvent.
In the dehydration step, to the reaction system, water-soluble
radical polymerization initiator is newly added, end a reducing
substance is also added. The water-soluble radical polymerization
initiator and the reducing substance are both preferably added to
the reaction system as an aqueous solution. Each occasion of the
addition of the water-soluble radical polymerization initiator and
the reducing substance is decided according to the residual water
rate of the reaction system. Specifically, the water-soluble
radical polymerization initiator is added to the reaction system at
any dehydration stage (first dehydration stage) when the residual
water rate of the reaction system is 50% or more, preferably 55% or
more, and more preferably 60% or more. On the other hand, the
reducing substance is added to the reaction system at any
dehydration stage (second dehydration stage) when the residual
water rate decreases from that at the first dehydration stage by
10% or more, preferably by 15% or more, and more preferably by 20%
or more. However, the second dehydration stage is preferably set in
the stage in which water remains in the reaction system.
Herein, the residual water rate of the reaction system refers to
the percentage of the mass of water remaining in the reaction
system based on the mass of the water-soluble ethylenically
unsaturated monomer used in the polymerization step, and is
calculated by the following formula (1). In the formula (1), "Mass
of Water Remaining in. Reaction System" means the total mass of
water present in the reaction system at the calculation of the
residual water rate, and is calculated by subtracting the mass of
water removed from the reaction system at the calculation of the
residual water rate from the amount of the material used in the
polymerization step, and if applicable, the addition amount of the
aqueous solutions such as the aqueous solution of the water-soluble
radical polymerization initiator and the aqueous solution of the
reducing substance added to the reaction system in the dehydration
step.
.times..times..times..times..times..times..times..times..times..times..ti-
mes..times..times..times..times..times..times..times..times..times..times.-
.times..times..times..times..times..times..times..times..times..times..tim-
es..times..times. ##EQU00003##
In the dehydration step, when the water-soluble radical
polymerization initiator and the reducing substance are added in
this order at the above-described stages, a part of the residual
monomers that are present together with the water-absorbent resin
precursor produced in the reaction system is polymerized by the
water-soluble radical polymerization initiator, and also, a part of
the residual monomers converted into another compound (derivative
of the residual monomers) by the reaction with the reducing
substance. Consequently, a water-absorbent resin in which the
amount of residual monomers is significantly reduced is obtainable.
The polymer of the residual monomers and the derivative of the
residual monomers generated herein are stable substances, and an
effect to the living body such as a human body, particularly, an
effect to the skin, is less as compared to the residual
monomers.
When the addition order of the water-soluble radical polymerization
initiator and the reducing substance is inversed, specifically,
when the reducing agent is added and then the water-soluble radical
polymerization initiator is added to the reaction system, among the
reducing substance added earlier, the residue that has failed to be
involved in the reaction with the residual monomers tends to
promote cleavage of the water-soluble radical polymerization
initiator to be added later (radical generation). Therefore, the
polymerization of the residual monomers in the reaction system is
less likely to progress, and consequently the content of the
residual monomers in the resulting water-absorbent resin is less
likely to decrease.
In addition, when the er-soluble radical polymerization initiator
is added after the residual water rate of the reaction system falls
below 50%, the polymerization of the residual monomers is less
likely to progress, then it becomes difficult to sufficiently
reduce the content of the residual monomers the intended
water-absorbent resin. Furthermore, when the reducing substance is
added after the residual water rate falls to only less than 10% as
compared to the first dehydration stage, the cleavage reaction
(radical generation) of the water-soluble radical polymerization
initiator added in advance tends to be extremely promoted, and
consequently, the polymerization of the residual monomers is less
likely to progress. As a result, it becomes difficult to
sufficiently reduce the content of the residual monomers in the
intended water-absorbent resin.
When the water-soluble radical polymerization initiator or the
reducing substance is added to the reaction system, it is necessary
to rapidly and smoothly progress the reaction of each additive with
the residual monomers, and therefore, heating is required. In this
regard, the heating temperature the reaction system in the
dehydration step is usually preferably set to 40 to 110.degree. C.
and more preferably set to 50 to 90.degree. C. In addition, the
reaction time necessary after the addition of each additive is
usually from 10 minutes to 3 hours or so. When the reaction system
reaches the second dehydration stage within the necessary reaction
time after the addition of the water-soluble radical polymerization
initiator, the reducing substance may be added even within the
reaction time.
Examples of the water-soluble radical polymerization initiator
added to the reaction system in the dehydration step include
persulfates such as potassium persulfate, ammonium persulfate and
sodium persulfate; peroxides such as methyl ethyl ketone peroxide,
methyl isobutyl ketone peroxide, di-t-butyl peroxide, t-butyl cumyl
peroxide, t-butylperoxy acetate, t-butylperoxy isobutylate,
t-butylperoxy pivalate and hydrogen peroxide; azo compounds such as
2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride,
2,2'-azobis[2-(N-allylamidino)propane]dihydrochloride,
2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochlori-
de,
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propiona-
mide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide] and
4,4'-azobis(4-cyanovaleric acid); and the like. Among these,
potassium persulfate, sodium persulfate or
2,2'-azobis[2-(N-phenylamidino)propane]dihydrochloride is
preferably used since they are easily available industrially and
have stable quality and high safety.
The water-soluble radical polymerization initiator may be used in
combination of two or more kinds.
The amount of the water-soluble radical polymerization initiator
added to the reaction system is preferably net to 0.01 to 0.15 mol
% of the total amount of the water-soluble ethylenically
unsaturated monomer used in the polymerization step. When the
addition amount is less than 0.01 mol %, sufficient result in
reducing residual monomers is possibly less likely to be obtained.
In contrast, when the addition amount exceeds 0.15 mol %,
water-absorption properties of the water-absorbent resin to be
obtained may be impaired.
In addition, examples of the reducing substance added to the
reaction system can include sulfurous acid and a salt thereof,
hydrogen sulfite and a salt thereof, phosphorous acid and a salt
thereof, hypophosphorous acid and a salt thereof, thiosulfuric acid
and a salt thereof, and the like. Among these, sulfurous acid or a
salt thereof, or hydrogen sulfite or a salt thereof is preferable
since they are easily available industrially and have high safety,
and their handling is easy.
The reducing substance may be used in combination of two or more
kinds.
The amount of the reducing substance added to the reaction system
is preferably set to 0.0001 to 0.002 mol % of the total amount of
the water-soluble ethylenically unsaturated monomer used in the
polymerization step. When the addition amount is less than 0.0001
mol %, a sufficient result in reducing residual monomers is
possibly less likely to be obtained. In contrast, when the addition
amount exceeds 0.002 mol %, water-absorption properties of the
water-absorbent resin to be obtained may be impaired.
In the production method of the present invention, the
water-absorbent resin precursor obtained in the polymerization step
can be subjected to a post-crosslinking treatment. Since the
water-absorbent resin obtainable by thereafter subjecting the
precursor to a post-crosslink ng treatment has increased
crosslinking density of a surface, the amount of water-soluble
substance is decreased, and water-absorption capacity under load is
increased.
The post-crosslinking treatment can be usually carried out in a
suitable stage in the dehydration step. However, it is usually
preferable to carry out the post-crosslinking treatment after a
reducing substance is added in the dehydration step and the
reaction thereof is progressed.
In the post-crosslinking treatment, a post-crosslinking agent is
reacted with the water-absorbent resin precursor. The usable
post-crosslinking agent is a polyfunctional post-crosslinking agent
that can be reacted with a carboxyl group of the water-absorbent
resin precursor, and examples thereof include compounds having two
or more reactive functional groups such as dials, trials or polyols
such as ethylene glycol, polyethylene glycol, propylene glycol,
polypropylene glycol, 1,4-butanediol, trimethylolpropane,
polyoxyethylene glycol, polyoxypropylene glycol, glycerin and
polyglycerin; diglycidyl ether compounds such as ethylene glycol
diglycidyl ether, polyethylene glycol diglycidyl ether, propylene
glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
glycerol diglycidyl ether and polyglycerol diglycidyl ether;
epihalohydrin compounds such as epichlorohydrin, epibromohydrin and
.alpha.-methylepichlorohydrin; and isocyanate compounds such as
2,4-tolylene diisocyanate and hexamethylene diisocyanate.
Among these, a diglycidyl ether compound is preferable since a
water-absorbent resin showing high water-absorption capacity under
load and excellent water absorption rate and having a smaller
amount of water-soluble substance is likely to be obtained.
Particularly, ethylene glycol diglycidyl ether, propylene glycol
diglycidyl ether, glycerol diglycidyl ether or polyethylene glycol
diglycidyl ether is preferable since water solubility is high and
handling properties as a crosslinking agent is fine. Among these,
ethylene glycol diglycidyl ether and propylene glycol diglycidyl
ether are more preferable since they can enhance swelling
performance of the resulting water-absorbent resin particles.
The post-crosslinking agent can be used in combination of two or
mote kinds.
The usage of the post-crosslinking agent can be variant depending
on the type of the post-crosslinking agent, but is usually
preferably set to 0.00001 to 0.01 mol, more preferably set to
0.00005 to 0.005 mol, and particularly preferably set to 0.0001 to
0.002 mol, relative to 1 mol of the water-soluble ethylenically
unsaturated monomer used in the polymerization step. When the usage
is less than 0.00001 mol, the crosslinking density of the
water-absorbent resin is less likely to increase, thus it becomes
difficult to reduce the water-soluble substance in the
water-absorbent resin and to increase water-absorption capacity
under load of the water-absorbent resin. In contrast, when the
usage of the post-crosslinking agent exceeds 0.01 mol, the
crosslinking reaction markedly progresses, thus water-retention
capacity of the water-absorbent resin may decrease.
The reaction of the water-absorbent resin precursor with the
post-crosslinking agent is preferably carried out in the presence
or ater. For this reason, it is preferred that water remains in the
reaction system when a post-crosslinking agent is added, and that a
post-crosslinking agent is added to the reaction system as an
aqueous solution. The amount of water (when the post-crosslinking
agent is added as an aqueous solution, this amount includes the
amount of water derived from the aqueous solution) in the reaction
system at the time when the post-crosslinking agent is added to the
reaction system can be adjusted depending on the factors such as
the type of the water-absorbent resin precursor, particle size, and
water content, but is usually preferably set to 5 to 300 parts by
mass, more preferably set to 10 to 100 parts by mass, and
particularly preferably set to 10 to 50 parts by mass, relative to
100 parts by mass of the water-soluble ethylenically unsaturated
monomer used in the polymerization step. When the amount of water
is less than 5 parts by mass, the crosslinking reaction is less
likely to progress in the water-absorbent resin precursor, and thus
it becomes difficult to increase water-absorption capacity under
load of the water-absorbent resin. In contrast, when the amount of
water exceeds 300 parts by mass, the crosslinking reaction is
excessively promoted, and thus water-retention capacity of the
water-absorbent resin may greatly decrease. The amount of water in
the reaction system means the total amount of water remaining in
the reaction system during dehydration and water supplied the
reaction system as necessary for post-crosslinking.
The objective water-absorbent resin can be obtained, after
completion of the reaction by a reducing substance in the
dehydration step or after completion of post-crosslinking
treatment, by removing a solvent such as hydrocarbon solvent and
water remaining in the system. For example, when a reversed-phase
suspension polymerization method is applied in the polymerization
step, a powdery water-absorbent resin is obtained by removing the
hydrocarbon solvent and water from the system. When an aqueous
polymerization method is applied, usually, an aggregated
water-absorbent resin is obtained, and it is preferred that this
water-absorbent resin is appropriately pulverized into a
powder.
Since a water-soluble radical polymerization initiator and a
reducing substance are added in a specific order at a particular
stage in the dehydration step, the polymerization or derivatization
of the residual monomers is well progressed. Therefore, the content
of the residual monomers in the water-absorbent resin obtainable by
the production method of the present invention can usually be a
trace amount of 100 ppm less, 90 ppm or less, or 80 ppm or
less.
The water-absorbent resin obtainable by the production method of
the present invention can be used in various fields of hygienic
materials such as disposable diapers and sanitary articles,
commodities such as pet sheets, agricultural materials such as
water-retaining materials and soil conditioners, and industrial
materials such as water blocking materials for electrical power
cable and communication cable and dew-catchers. Since the content
of residual monomers is a trace amount, the water-absorbent resin
is safe for the human body, particularly for the skin, and thus is
particularly suitably used in a hygienic material.
When the powdery water-absorbent resin obtainable by the production
method of the present invention is intended to use in a hygienic
material, the mass average particle size is preferably adjusted to
200 to 600 .mu.m, more preferably adjusted to 250 to 500 .mu.m, and
particularly preferably adjusted to 300 to 400 .mu.m. In the case
of the reversed-phase suspension polymerization method, the mass
average particle size can be adjusted to a preferred range by the
control of polymerization conditions, the conditioning of
pulverization, classification, and the like.
The water-absorbent resin obtainable by the production method of
the present invention has a high absorption rate of saline
solution, which can be within 60 seconds, or within 55 seconds or
within 50 seconds, by setting the mass average particle size within
the above range. Therefore, when the water-absorbent resin is used
in a hygienic material, the amount of re-wet can be suppressed
owing to the high diffusibility of urine and blood. When the mass
average particle size of the water-absorbent resin is less than 200
.mu.m, the presence of small particles becomes greater, and thus
handling properties of the water-absorbent resin may be
deteriorated due to dusting and the like. Also, when used as a
hygienic material, gel blocking is likely to be caused at the time
of water absorption, resulting in the possibility of lower
diffusibility of water or increase the amount of re-wet. In
contrast, when the mass average particle size exceeds 600 .mu.m,
the water-absorption rate decreases. Therefore, when used in a
hygienic material, urine and blood cannot be rapidly absorbed, and
thus their leakage from the material may happen.
The absorption rate of saline solution described above is a value
measured according to the method described in Examples set forth
below.
The water-absorbent resin having the mass average particle size
adjusted to the above range is likely to achieve the
water-absorption properties required in a hygienic material.
Specifically, this water-absorbent resin shows a retention capacity
of saline solution of 40 to 60 g/g and an absorption capacity of
saline solution under a load of 4.14 kPa of 20 ml/g or more. The
larger the numerical value of the absorption capacity of saline
solution under a load of 4.14 kPa, the smaller the amount of re-wet
of urine or blood even when a pressure is applied to a hygienic
material. The retention capacity of saline solution and the
absorption capacity of saline solution under a load of 4.14 kPa can
be measured according to the corresponding method described in
Examples set forth below.
The numerical values of the water-absorption rate of saline
solution, the water-retention capacity of saline solution and the
absorption capacity of saline solution under a load of 4.14 kPa
described above are the properties generally achieved when the mass
average particle size of the water-absorbent resin obtained by the
well-known production method of polymerizing a polymerizable
component containing a water-soluble ethylenically unsaturated
monomer dissolved in water using a water-soluble azo-type radical
polymerization initiator and removing water from the reaction
system by heating, is adjusted to the range as described above,
particularly when the precursor is subjected to the above-described
post-crosslinking treatment. Therefore, according to the production
method of the present invention, the content of the residual
monomers in a water-absorbent resin obtained by well-known
production method can be reduced without impairing the
water-absorption capacity (water-absorbing properties).
In the production method of the present invention, when the
water-absorbent resin precursor is subjected to a post-crosslinking
treatment, the obtained water-absorbent resin has increased
crosslinking density of a surface, and thus the water-soluble
substance is decreased. Therefore, when used in a hygienic
material, "skin irritation" and "sliminess" due to effusion of a
water-soluble substance can be suppressed. When the amount of the
post-crosslinking agent used at the time of post-crosslinking
treatment is set to the range as described above, the volume of a
water-soluble substance in the water-absorbent resin can be usually
20% by mass or less or 15% by mass or less in accordance with the
amount of the post-crosslinking agent. The volume of a
water-soluble substance is the value measured by the method
described in Examples set forth below.
As the hygienic material using the water-absorbent resin obtained
by the production method of the present invention, one formed by
interposing an absorbent material containing the water-absorbent
resin between a liquid-permeable sheet and a liquid-impermeable
sheet is preferable.
The liquid-permeable sheet used herein may be, for example, a
nonwoven fabric or a porous sheet, made of polyethylene resin,
polypropylene resin, polyester resin or polyamide resin. The
liquid-impermeable sheet may be, for example, a film made of a
synthetic resin or a composite material composed of a synthetic
resin and a nonwoven fabric. Examples of the synthetic resin usable
for the film include polyethylene resin, polypropylene resin and
polyvinyl chloride resin.
The absorbent material used herein may be substantially made from a
water-absorbent resin, but is usually preferably a complex with a
hydrophilic fiber. Examples of this complex preferably include
those having a mixing structure in which a water-absorbent resin
and a hydrophilic fiber are uniformly blended, a sandwich structure
in which a water-absorbent resin is retained between layered
hydrophilic fibers, or a packaging structure in which a mixture of
a water-absorbent resin and a hydrophilic fiber is wrapped with a
packaging sheet having liquid permeability, such as tissue paper.
Examples of the hydrophilic fiber used in the complex include
cellulose fibers such as a cotton-like pulp obtained from wood, a
mechanical pulp, a chemical pulp and a semi-chemical pulp;
artificial cellulose fibers such as rayon and acetate; and the
like. The hydrophilic fiber may contain synthetic fibers such as
polyamide resin fiber, polyester resin, fiber and polyolefin resin
fiber.
EXAMPLES
The present invention will be specifically described below by way
of examples and comparative examples, but the present invention is
not limited to these examples and the like.
Example 1
<Polymerization Step>
A 1000 mL five-necked cylindrical round-bottom flask, equipped with
an agitator, a reflux condenser, a dropping funnel, a thermometer
and a nitrogen gas inlet tube was charged with 340 g of n-heptane,
and 0.83 g of a sucrose fatty acid ester having an HLB of 3.0
(manufactured by Mitsubishi Chemical Corporation under the trade
name of "S-370") was added. After the sucrose fatty acid ester was
dissolved by heating while being dispersed, the mixture was cooled
to 55.degree. C.
Separately from the above, a 500 mL Erlenmeyer flask was charged
with 92 g (1.03 mol) of an 80.5% by mass aqueous solution of
acrylic acid. Thereto was added dropwise 147.6 g (0.77 mol) of a
20.9% by mass aqueous solution of sodium hydroxide while externally
cooling the flask, to neutralize 75 mol % of acrylic acid. Further,
0.0552 g (0.00020 mol) of
2,2'-azobis(2-amidinopropane)dihydrochloride as water-soluble
azo-type radical polymerization initiator and 0.0102 g (0.000059
mol) of ethylene glycol diglycidyl ether as an
internal-crosslinking agent were added, to prepare an aqueous
monomer solution for the first-stage polymerization.
Also, in a separate 500 ml Erlenmeyer flask, 128.8 g (1.44 mol) of
an 80.5% by mass aqueous solution of acrylic acid was charged, and
thereto was added dropwise 160.56 g (1.08 mol) of a 26.9% by mass
aqueous solution of sodium hydroxide while externally cooling the
flask, to neutralize 75 mol % of acrylic acid. Further, 0.0772 g
(0.00028 mol) of 2,2'-azobis(2-amidinopropane)dihydrochloride as a
water-soluble azo-type radical polymerization initiator and 0.0116
g (0.000067 mol) of ethylene glycol diglycidyl ether as an
internal-crosslinking agent were added, to prepare an aqueous
monomer solution for the second-stage polymerization. This aqueous
monomer solution for the second-stage polymerization was cooled
using an ice-water bath.
The total amount of the aqueous monomer solution for the
first-stage polymerization was added to the five-necked cylindrical
round-bottom flask while stirring and then dispersed. The inside of
the flask was sufficiently replaced with nitrogen and then heated
and the bath temperature was kept at 70.degree. C. to carry out
polymerization reaction for 1 hour. After the resulting polymeric
slurry liquid was cooled to room temperature, the total amount of
the aqueous monomer solution for the second-stage polymerization
was added to the polymerized slurry liquid. The inside of the flask
was again sufficiently replaced with nitrogen and then heated, and
the bath temperature was kept at 70.degree. C. to carry out the
second-stage polymerization reaction for 2 hours.
<Dehydration Step>
After the completion of the second-stage polymerization, the
five-necked cylindrical round-bottom flask was heated with an oil
bath of 120.degree. C., and azeotropic distillation of water and
n-heptane in the reaction system was performed, thereby removing
174.8 g of water off the system while refluxing n-heptane (it was
the first dehydration stage, and the residual water rate was 62%).
Herein, an aqueous solution obtained by dissolving 0.3092 g (0.0011
mol) of potassium persulfate in 15.0 g of water was added, and the
reaction system was kept at 80.degree. C. for 20 minutes.
Furthermore, azeotropic distillation of water and n-heptane was
performed, thereby removing 43.7 g of water off the system while
refluxing n-heptane (it was the second dehydration stage, and the
residual water rate was 49%). Herein, an aqueous solution obtained
by dissolving 0.2208 g (0.00175 mol) of sodium sulfite in 10.0 g of
water was added, and the reaction system was kept at 80.degree. C.
for 20 minutes. Subsequently, azeotropic distillation of water and
n-heptane was performed, thereby removing 62.3 g of water off the
system while refluxing n-heptane (the residual water rate was 25%).
Thereafter, 4.415 g (0.0007 mol) of a 2% aqueous solution of
ethylene glycol diglycidyl ether as a post-crosslinking agent was
added, and the reaction system was kept at 80.degree. C. for 2
hours. Furthermore, n-heptane and water were vaporized to have the
reaction system dried, thereby obtaining 228.2 g of a
water-absorbent resin in which spherical particles were
agglomerated.
Example 2
The same procedures were carried out as in Example 1 except that
the amount of potassium persulfate added in the first dehydration
stage was changed from 0.3092 g to 0.2319 g (0.0009 mol), to obtain
228.5 g of a water-absorbent resin in which spherical particles
were agglomerated.
Example 3
The same procedures were carried out as in Example 1 except that
the amount of sodium sulfite added in the second dehydration stage
was changed from 0.2208 g to 0.1105 g (0.00088 mol), to obtain
228.8 g of a water-absorbent resin in which spherical particles
were agglomerated.
Example 4
The same procedures were carried out as in Example 1 except that
0.3092 g of potassium persulfate added in the first dehydration
stage was changed to 0.2724 g (0.0011 mol) of sodium persulfate, to
obtain 228.8 g of a water-absorbent resin in which spherical
particles were agglomerated.
Example 5
The same procedures were carried out as in Example 1 except that
0.2208 g of sodium sulfite added in the second dehydration stage
was changed to 0.1823 g (0.00175 mol) of sodium bisulfite, to
obtain 227.8 g of a water-absorbent resin in which spherical
particles were agglomerated.
Example 6
The same procedures were carried out as in Example 1 except that
0.0829 g (0.00020 mol) of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate
was used in place of 0.0552 g (0.00020 mol) of
2,2'-azobis(2-amidinopropane)dihydrochloride as a water-soluble
azo-type radical polymerization initiator in the aqueous monomer
solution for the first-stage polymerization, and 0.1160 g (0.00028
mol) of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate
was used in place of 0.0772 g (0.00028 mol) of
2,2'-azobis(2-amidinopropane)dihydrochloride as water-soluble
azo-type radical polymerization initiator in the aqueous monomer
solution for the second-stage polymerization, to obtain 228.4 g of
a water-absorbent resin in which spherical particles were
agglomerated.
Example 7
The same procedures were carried out as in Example 1 except that
the dehydration amount in the first dehydration stage (the amount
of water removed off before adding potassium persulfate) was
changed from 174.8 g (the residual water rate was 62%) to 196.7 g
(the residual water rate was 52%), and the amount of water removed
off the system after adding sodium sulfite and being kept at
80.degree. C. for 20 minutes was changed from 62.3 g (the residual
water rate was 25%) to 40.4 g (the residual water rate was 25%), to
obtain 228.0 g of a water-absorbent resin in which spherical
particles were agglomerated. In this case, the residual water rate
at the second dehydration stage was 39%.
Comparative Example 1
The polymerization step was carried out in the same manner as in
Example 1. After the completion of the second-stage polymerization
in the polymerization step, the five-necked cylindrical
round-bottom flask was heated with an oil bath of 120.degree. C.,
and azeotropic distillation of water and n-heptane in the reaction
system was performed, thereby removing 225.8 g of water off the
system while refluxing n-heptane (the residual water rate was 25%).
Thereafter, 4.415 g (0.0007 mol) of a 2% aqueous solution of
ethylene glycol diglycidyl ether was added, and the reaction system
was kept at 80.degree. C. for 2 hours. Furthermore, n-heptane was
vaporized to have the reaction system dried, thereby obtaining
228.2 g of a water-absorbent resin in which spherical particles
were agglomerated.
Comparative Example 2
The polymerization step was carried out in the same manner as in
Example 1. After the completion of the second-stage polymerization
in the polymerization step, the five-necked cylindrical
round-bottom flask was heated with an oil bath of 120.degree. C.,
and azeotropic distillation of water and n-heptane in the reaction
system was performed, thereby removing 218.5 g of water off the
system while refluxing n-heptane (the residual water rate was 42%).
Herein, an aqueous solution obtained by dissolving 0.2208 g
(0.00175 mol) of sodium sulfite in 10.0 g of water was added, and
the reaction system was kept at 80.degree. C. for 20 minutes.
Subsequently, azeotropic distillation of water and n-heptane was
performed, thereby removing 47.3 g of water off the system while
refluxing n-heptane (the residual water rate was 25%). Thereafter,
4.415 g (0.0007 mol) of a aqueous solution of ethylene glycol
diglycidyl ether was added, and the reaction system was kept at
80.degree. C. for 2 hours. Furthermore, n-heptane and water were
vaporized to have the reaction system dried, thereby obtaining
227.8 g of water-absorbent resin in which spherical particles were
agglomerated.
Comparative Example 3
The same procedures were carried out as in Comparative Example 2
except that the amount of sodium sulfite was changed from 0.2208 g
to 0.6624 g (0.00525 mol), to obtain 226.8 g of a water-absorbent
resin in which spherical particles were agglomerated.
Comparative Example 4
The polymerization step was carried out in the same manner as in
Example 1. After the completion of the second-stage polymerization
in the polymerization step, the five-necked cylindrical
round-bottom flask was heated with an oil bath of 120.degree. C.,
and azeotropic distillation of water and n-heptane in the reaction
system was performed, thereby removing 174.8 g of water off the
system while refluxing n-heptane (the residual water rate was 62%).
Herein, an aqueous solution obtained by dissolving 0.3092 g (0.0011
mol) of potassium persulfate in 15.0 g of water was added, and the
reaction system was kept at 80.degree. C. for 20 minutes.
Subsequently, azeotropic distillation of water and n-heptane was
performed, thereby removing 96.0 g of water off the system while
refluxing n-heptane (the residual water rate was 25%). Thereafter,
4.415 g (0.0007 mol) of a 2% aqueous solution of ethylene glycol
diglycidyl ether was added, and the reaction system was kept at
80.degree. C. for 2 hours. Furthermore, n-heptane and water were
vaporized to have the reaction system dried, thereby obtaining
228.3 g of a water-absorbent resin in which spherical particles
were agglomerated.
Comparative Example 5
The same procedures were carried out as in Comparative Example 4
except that the amount of potassium persulfate was changed from
0.3092 g to 1.1043 g (0.0041 mol), to obtain 225.9 g of a
water-absorbent resin in which spherical particles were
agglomerated.
Comparative Example 6
The polymerization step was carried out in the same manner as in
Example 1. After the completion of the second-stage polymerization
in the polymerization step, an aqueous solution obtained by
dissolving 1.1043 g (0.0041 mol) of potassium persulfate in 15.0 g
of ter was added to the reaction system. Then, the flask heated
with an oil bath of 120.degree. C., and azeotropic distillation of
water and n-heptane was performed, thereby removing 270.8 g of
water off the system while refluxing n-heptane (the residual water
rate was 25%). Herein, 4.415 g (0.0007 mol) of a 2% aqueous
solution of ethylene glycol diglycidyl ether was added, and the
reaction system was kept at 80.degree. C. for 2 hours. Furthermore,
n-heptane and water were vaporized to have the reaction system
dried, thereby obtaining 228.6 g of a water-absorbent resin in
which spherical particles were agglomerated.
Comparative Example 7
The polymerization step was carried out in the same manner as in
Example 1. After the completion of the second-stage polymerization
in the polymerization step, the five-necked cylindrical
round-bottom flask was heated with an oil bath of 120.degree. C.,
and azeotropic distillation of water and n-heptane in the reaction
system was performed, thereby removing 174.8 g of water off the
system while refluxing n-heptane (the residual water rate was 62%).
Herein, an aqueous solution obtained by dissolving 0.3092 g (0.0011
mol) of potassium persulfate in 15.0 g of water and an aqueous
solution obtained by dissolving 0.2208 g (0.00175 mol) of sodium
sulfite in 10.0 g of water were added at the same time, and the
reaction system was kept at 80.degree. C. for 20 minutes. Then,
azeotropic distillation of water and n-heptane was performed,
thereby removing 106.0 g of water off the system while refluxing
n-heptane (the residual water rate was 25%). Thereafter, 4.415 g
(0.0007 mol) of a 2% aqueous solution of ethylene glycol diglycidyl
ether was added, and the reaction system was kept at 80.degree. C.
for 2 hours. Furthermore, n-heptane and water were vaporized to
have the reaction system dried, thereby obtaining 227.0 g of a
water-absorbent resin in which spherical particles were
agglomerated.
Comparative Example 8
The polymerization step was carried out in the same manner as in
Example 1. After the completion of the second-stage polymerization
in the polymerization step, the five-necked cylindrical
round-bottom flask was heated with an oil bath of 120.degree. C.,
and azeotropic distillation of water and n-heptane in the reaction
system was performed, thereby removing 174.8 g of water off the
system while refluxing n-heptane (it was the first dehydration
stage, and the residual water rate was 62%). Herein, an aqueous
solution obtained by dissolving 0.2208 g (0.00175 mol) of sodium
sulfite in 10.0 g of water was added, and the reaction system was
kept at 80.degree. C. for 20 minutes. Furthermore, azeotropic
distillation of water and n-heptane was performed, thereby removing
43.7 g of water off the system while refluxing n-heptane (it was
the second dehydration stage, and the residual water rate was 42%).
Herein, an aqueous solution obtained by dissolving 0.3092 g (0.0011
mol) of potassium persulfate in 15.0 g of water was added, and the
reaction system was kept at 80.degree. C. for 20 minutes.
Subsequently, azeotropic distillation of water and n-heptane was
performed, thereby removing 62.3 g of water off the system while
refluxing n-heptane (the residual water rate was 25%). Thereafter,
4.415 g (0.0007 mol) of a 2% aqueous solution of ethylene glycol
diglycidyl ether was added, and the reaction system was kept at
80.degree. C. for 2 hours. Furthermore, n-heptane and water were
vaporized to have the reaction system dried, thereby obtaining
228.3 g of a water-absorbent resin in which spherical particles
were agglomerated.
Evaluation
With respect to the water-absorbent resins obtained in the
respective examples and comparative examples, retention capacity of
saline solution, water-absorption capacity under load, content of
residual monomers, absorption rate of saline solution and
water-soluble substance were measured by the following methods. The
results are shown in Table 1.
(Retention Capacity of Saline Solution)
In a 500 mL beaker, 500 g of a 0.9% by mass aqueous salt solution
(physiological saline) was charged, and then 2.0 g of the
water-absorbent resin was dispersed while stirring at 600 r/min. so
as not to generate an unswollen lump. The physiological saline was
left under stirring for 30 minutes so that the water-absorbent
resin was sufficiently swollen, then the whole content of the
beaker was poured into a cotton bag (cotton-broad cloth No. 60,
width 100 mm.times.length 200 mm). The cotton bag of which upper
part was tied up with a rubber band was dehydrated for 1 minute
with a dehydrator (manufactured by Kokusan Enshinki Co., Ltd. under
the product number "H-122") set to have a centrifugal force of 167
G, then the mass Wa (g) of the cotton bag containing the swollen
gel after the dehydration was measured. In addition, the same
procedures were carried out without adding the water-absorbent
resin to physiological saline, and the blank mass Wb (g) of the
cotton bag upon wetting was measured. Then, the retention capacity
of saline solution was calculated by the following formula.
.times..times..times. ##EQU00004##
.times..times..times..times..times..times..times..times..times..times..ti-
mes..times..times..times..times..times..times..times..times..times..times.-
.times..times..times. ##EQU00004.2## (Water-Absorption Capacity
Under Load)
Using a measuring apparatus 100 schematically shown in FIG. 1, the
measurement was made. In the drawing, the measuring apparatus 100
includes a burette section 1, a conduit 2, a measurement stage 3,
and a measurement section 4 placed on the measurement stage 3. The
burette section 1 includes a burette 10. In this burette 10, the
upper portion is closable by a rubber stopper 14, and an air inlet
tube 11 and a cock 12 are connected to the lower portion. The air
inlet tube 11 has a cock 13 at the tip. The conduit 2 has an inner
diameter of 6 mm, and connects the cock 12 of the burette section 1
with the measurement stage 3. The height of the measurement stage 3
is vertically adjustable. The measurement stage 3 is provided with
a hole (conduit port) having a diameter of 2 mm at the center, to
which one end of the conduit 2 is connected. The measurement
section 4 includes a cylinder 40 made of plexiglass, a polyamide
mesh 41 bonded to the bottom of the cylinder 40, and a weight 42
which is vertically movable in the cylinder 40. The cylinder 40 can
be disposed on the measurement stage 3 and the inner diameter
thereof is 20 mm. The sieve opening size of the polyamide mesh 41
is 75 .mu.m (200 mesh). The weight 42 has a diameter of 19 mm and a
mass of 119.6 g. As described below, the weight 42 is used for
applying a load of 4.14 kPa to a water-absorbent resin 5 spread
uniformly over the polyamide mesh 41.
The water-absorption capacity under load by this measuring
apparatus 100 was measured in a room at 25.degree. C. The specific
procedure is as follows. First, the cocks 12 and 13 of the burette
section 1 were closed and 0.9% by mass salt solution (physiological
saline) adjusted to 25.degree. C. was charged from the upper
portion of the burette 10. Next, the upper portion of the burette
10 was closed by the rubber stopper 14, and the cocks 12 and 13
were opened. Then, the height of the measurement stage 3 was
adjusted so that the water level of physiological saline coming out
from the conduit port of the measurement stage 3 through the
conduit 2 is even with the upper surface of the measurement stage
3. In the measurement section 4, 0.10 g of the water-absorbent
resin 5 was uniformly spread over the polyamide mesh 41 in the
cylinder 40, and the weight 42 was placed on the water-absorbent
resin 5. Then, the cylinder 40 was disposed on the measurement
stage 3 so that an axis line thereof agrees with the conduit port
of the measurement stage 3.
A decrease in the amount of physiological saline (i.e., amount of
physiological saline absorbed in the water-absorbent resin 5) Wc
(ml) in the burette 10 was read 60 minutes after the beginning of
absorption of physiological saline from the conduit 2 by the
water-absorbent resin 5. The water-absorption capacity under load
of the water-absorbent resin 5 was calculated by the following
formula.
.times..times..times. ##EQU00005##
.times..times..times..times..times..times..times..times..times..times..ti-
mes..times..times..times..times..times..times..times..times..times..times.-
.times..times..times. ##EQU00005.2## (Content of Residual
Monomers)
In a 500 mL beaker, 500 g of a 0.9.degree. by mass aqueous salt
solution (physiological saline) was charged, then 2.0 g of the
water-absorbent resin was added, and the mixture was stirred for 60
minutes. The content in the beaker was passed through a JIS (Japan
Industrial Standard) standard sieve with a sieve opening of 75
.mu.m, then filtrated with a filter paper (No. 3 manufactured by
ADVANTEC), to separate a water-absorbed gel and an extraction
liquid (physiological saline). The amount of monomers dissolved in
the obtained extraction liquid was measured by high-performance
liquid chromatography. The monomers to be measured herein were
acrylic acid and alkali metal salts thereof. The measured value was
converted into the value per mass of the water-absorbent resin, and
was defined as the content of residual monomers (ppm).
(Absorption Rate of Saline Solution)
The measurement was carried out in a room adjusted to 25.degree.
C..+-.1.degree. C. A magnetic stirrer bar (8 mm.phi..times.30 mm
with no ring) was put in a 100 mL beaker in which 50.+-.0.1 g of
physiological saline had been charged. Then, this beaker was
immersed in a constant-temperature water bath to adjust the
solution temperature to 25.+-.0.2.degree. C. Next, the beaker was
placed on a magnetic stirrer (manufactured by Iuchi under the
product number "HS-30D") to generate a vortex in physiological
saline at a rotational speed of 600/min. Then, 2.0.+-.0.002 g of
the water-absorbent resin was quickly added to the beaker. The
elapsed time (seconds) from the point of the completion of adding
the water-absorbent resin to the point where a vortex on the liquid
surface vanished was measured using a stopwatch, which was defined
as an absorption rate of saline solution of water-absorbent resin
particles.
(Water-Soluble Substance)
A magnetic stirrer bar (8 mm.phi..times.30 mm with no ring) was put
in a 500 mL beaker in which 500.+-.0.1 g of physiological saline
had been charged. Then, this beaker was placed on a magnetic
stirrer (manufactured by Iuchi under the product number "HS-30D").
The magnetic stirrer bar was adjusted so as to have a rotational
speed of 600 r/min., and also adjusted so that the bottom of the
vortex generated by the rotation thereof came close thereto.
Next, the water-absorbent resin was classified using two kinds of
standard sieves complying with JIS-Z8801-1982 (one has the sieve
opening of 500 .mu.m, and the other has that of 300 .mu.m), to
adjust the particle size of the water-absorbent resin to 500 .mu.m
or less and 300 .mu.m or more. Then, 2.0.+-.0.002 g of the
water-absorbent resin was dispersed in the solution in the beaker
by quickly pouring it between the center of vortex generated in the
beaker and the side-wall of the beaker, and was stirred for 3
hours. Then, the aqueous dispersion of the water-absorbent resin
after stirring for 3 hours was filtered with a standard sieve
(sieve opening: 75 .mu.m) and the resulting filtrate was further
subjected to suction filtration using a Kiriyama type funnel with
the filter paper of No. 6. In a 100 mL beaker heat-processed
beforehand to be a constant weight, 80.+-.0.1 g of the resulting
filtrate was poured. The filtrate was dried up with a hot air drier
(product of ADVANTEC) at 140.degree. C. until a constant weight was
attained, and the mass Wd (g) of the solid content of the filtrate
was measured. Also, the same procedures as the above were carried
out without using the water-absorbent resin, and the mass We (g) of
the solid content of the filtrate was measured. The volume of the
water-soluble substance in the water-absorbent resin as calculated
on the basis of the following formula.
.times..times..times. ##EQU00006##
.times..times..times..times..times..times..times..times..times..times..ti-
mes..times. ##EQU00006.2##
TABLE-US-00001 TABLE 1 Retention Capacity Water-Absorption Content
of Absorption Rate Water-Soluble of Saline Capacity Under Residual
of Saline Solution Substance Solution (g/g) Load (ml/g) Monomers
(ppm) (Seconds) (% by Mass) Example 1 42 20 32 39 12 Example 2 45
21 70 41 14 Example 3 41 23 75 40 12 Example 4 44 20 40 41 13
Example 5 41 23 46 39 11 Example 6 42 24 50 40 12 Example 7 40 20
60 40 11 Comparative 42 24 1448 41 12 Example 1 Comparative 42 22
337 41 11 Example 2 Comparative 43 13 94 40 13 Example 3
Comparative 44 16 400 39 12 Example 4 Comparative 43 16 185 40 11
Example 5 Comparative 42 18 118 40 12 Example 6 Comparative 43 17
220 42 13 Example 7 Comparative 42 22 308 40 12 Example 8
As is apparent from Table 1, the water-absorbent resins obtained in
Examples 1 to 7 all demonstrate favorable water-absorption capacity
and reduced content of residual monomers. By contrast, favorable
water-absorption capacity does not coexist with reduced content of
residual monomers with respect to the water-absorbent resins
obtained in Comparative Examples 1 to 8.
The present invention can be carried out in other specific forms
without departing from the spirit or essential properties thereof.
The above embodiment and example are therefore to be considered in
all respects as illustrative and not restrictive. The scope of the
present invention is indicated by the appended claims rather than
by the foregoing description. All changes and modifications which
come within the range of equivalency of the claims are therefore
intended to be included within the scope of the present
invention.
* * * * *